精密合成による環拡張ポルフィリンの機能設計

• Project/Area Number: 13J00514
• Research Category: Grant-in-Aid for JSPS Fellows
• Allocation Type: Single-year Grants
• Section: 国内
• Research Field: Organic chemistry
• Research Institution: Kyoto University
• Principal Investigator: 森 裕貴 京都大学, 理学研究科, 特別研究員(DC1)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥3,000,000 (Direct Cost: ¥3,000,000); Fiscal Year 2015: ¥1,000,000 (Direct Cost: ¥1,000,000); Fiscal Year 2014: ¥1,000,000 (Direct Cost: ¥1,000,000); Fiscal Year 2013: ¥1,000,000 (Direct Cost: ¥1,000,000)
• Keywords: ポルフィリン / 環拡張ポルフィリン / π拡張ポルフィリン / ヘキサフィリン / らせん共役 / オリゴチオフェン / 近赤外色素 / 金属錯体 / 縮環 / アヌレノアヌレン / ハイブリッド / ポルフィリンテープ

Outline of Annual Research Achievements

本研究において申請者は１および２年度目に、１）複数の共役系を有する分子内架橋型環拡張ポルフィリンの合成と物性、２）ポルフィリン－ヘキサフィリンハイブリッド多量体の合成と物性、３）非環状らせん共役系を有するオリゴチエニル置換２６πヘキサフィリンの合成と物性、４）５，２０－ピロリル置換２６πヘキサフィリンおよびその金属二核錯体の合成と物性、といったテーマで研究を行い、新規な環拡張ポルフィリンの合成と物性評価を通じて様々な知見を得てきた。なかでも環拡張ポルフィリンのπ電子系の拡張とその近赤外光吸収スペクトルの長波長シフトの相関に関して得られた知見は非常に興味深く、３年度目においては５）近赤外領域に強い光吸収を示すメゾオリゴチエニル置換ポルフィリンの合成と物性、６）電子不足ポルフィリンテープ３量体および４量体の合成と物性、といったように、得られた知見を通常のポルフィリン類縁体への応用と展開を行った。これら５）および６）で得られた知見は一般性が高く、今後申請者が所属する研究室においてもさらに応用がなされ、体系だった研究が展開されることが期待される。
また３年度目は上記のメインテーマ５）および６）に加えて、自身の研究１）から６）に関連する共同研究などにも精力的に参画し、原著論文９報告を発表した。加えて従来通り各学会においても積極的に参加し、２件の研究発表を行った。

Research Progress Status

27年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

27年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] A very rapid electronic relaxation process in a highly conjugated Zn(II)porphyrin–[26]hexaphyrin–Zn(II)porphyrin hybrid tape (2016)
  • Author(s): S. Lee, H. Mori, T. Lee, M. Lim, A. Osuka, and D. Kim
  • Journal Title: Phys. Chem. Chem. Phys. Volume: 18 Issue: 4 Pages: 3244-3249
  • DOI: 10.1039/c5cp07417g
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Switchable π-Electronic Network of Bis(α-oligothienyl)-substituted Hexaphyrins between Helical versus Rectangular Circuit (2016)
  • Author(s): Juwon Oh, Hirotaka Mori, Young Mo Sung, Woojae Kim, Atsuhiro Osuka, Dongho Kim
  • Journal Title: Chemical Science Volume: 7 Issue: 3 Pages: 2239-2245
  • DOI: 10.1039/c5sc04263a
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] meso-meso Directly-Linked Trimeric and Pentameric Electron-Deficient Porphyrin-Hexaphyrin Hybrid Arrays (2016)
  • Author(s): Hirotaka Mori, Atsuhiro Osuka
  • Journal Title: Journal of Porphyrins and Phthalocyanines Volume: 印刷中 Issue: 01n04 Pages: 245-253
  • DOI: 10.1142/s1088424616500024
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] An Ethyne-bridged Porphyrin-Hexaphyrin-Porphyrin Triad That Undergoes A Thermal Transannular Cyclization (2016)
  • Author(s): Kazuma Honjo, Hirotaka Mori, Atsuhiro Osuka
  • Journal Title: Journal of Asian Organic Chemistry Volume: 5 Issue: 2 Pages: 196-200
  • DOI: 10.1002/ajoc.201500509
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Trimeric and Tetrameric Electron-Deficient Porphyrin Tapes (2016)
  • Author(s): Hirotaka Mori, Taeyeon Kim, Dongho Kim, Atsuhiro Osuka
  • Journal Title: Chemistry -An Asian Journal Volume: 印刷中 Issue: 9 Pages: 1454-1463
  • DOI: 10.1002/asia.201600241
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] A Stable Organic π-Radical of a Zinc(II)-Copper(I)-Zinc(II) Complex of Decaphyrin (2015)
  • Author(s): Y. Tanaka
  • Journal Title: Angew. Chem. Int. Ed. Volume: 54 Issue: 37 Pages: 10908-10911
  • DOI: 10.1002/anie.201505130
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] 5,20-Di(pyridin-2-yl)-[28]Hexaphyrin(1.1.1.1.1.1): A Stable Huckel Antiaromatic Hexaphyrin Stabilized by Intramolecular Hydrogen Bonding and Protonation Induced Conformational Twist to Gain Mobius Aromaticity (2015)
  • Author(s): Koji Naoda, Hirotaka Mori, Juwon Oh, Kyu Hyung Park, Dongho Kim, Atsuhiro Osuka
  • Journal Title: Journal of Organic Chemistry Volume: 80 Issue: 23 Pages: 11726-11733
  • DOI: 10.1021/acs.joc.5b01348
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Switching between Aromatic and Antiaromatic 1,3-Phenylene-Strapped [26]- and [28]Hexaphyrins upon Passage to the Singlet Excited State (2015)
  • Author(s): Y. M. Sung, J. Oh, W. Kim, H. Mori, A. Osuka, and D. Kim
  • Journal Title: J. Am. Chem. Soc Volume: 137 Issue: 37 Pages: 11856-11859
  • DOI: 10.1021/jacs.5b04047
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Synthesis of [n]Cyclo-5,15-porphyrinylene-4,4'-biphenylenes Displaying Size-dependant Excitation Energy Hopping (2015)
  • Author(s): Hua-Wei Jiang, Takayuki Tanaka, Taeyeon Kim, Young Mo Sung, Hirotaka Mori, Dongho Kim, and Atsuhiro Osuka
  • Journal Title: Angewandte Chemie International Edition Volume: 54 Issue: 50 Pages: 15197-15201
  • DOI: 10.1002/anie.201507822
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] 5,20-Bis(α-Oligothienyl)-Substituted [26]Hexaphyrins(1.1.1.1.1.1): 26π Aromatic Hexaphyrin Circuit versus Acyclic Helical Conjugation (2015)
  • Author(s): Hirotaka Mori, Masaaki Suzuki, Woojae Kim, Jong Min Lim, Dongho Kim, Atsuhiro Osuka
  • Journal Title: Chemical Science Volume: 6 Issue: 3 Pages: 1696-1700
  • DOI: 10.1039/c4sc03394a
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] meso-meso Linked Porphyrin–[26]Hexaphyrin–Porphyrin Hybrid Arrays and Their Triply Linked Tapes Exhibiting Strong Absorption Bands in NIR Region (2015)
  • Author(s): Hirotaka Mori, Takayuki Tanaka, Sangsu Lee, Jong Min Lim, Dongho Kim, Atsuhiro Osuka
  • Journal Title: Journal of the American Chemical Society Volume: 137 Issue: 5 Pages: 2097-2106
  • DOI: 10.1021/ja5130034
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Cyclic 2,12-Porphyrinylene Nanorings As a Porphyrin Analogue of Cycloparaphenylenes (2015)
  • Author(s): Hua-Wei Jiang, Takayuki Tanaka, Hirotaka Mori, Kyu Hyung Park, Dongho Kim, Atsuhiro Osuka
  • Journal Title: Journal of the American Chemical Society Volume: 137 Issue: 6 Pages: 2219-2222
  • DOI: 10.1021/ja513102m
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Bis-Metal Complexes of 5,20-Bis(5-formyl-2-pyrrolyl) [26]Hexaphyrin(1.1.1.1.1.1) Exhibiting Strong NIR Absorptions (2015)
  • Author(s): Hirotaka Mori, Atsuhiro Osuka
  • Journal Title: Chemistry – A European Journal Volume: 未確定 Issue: 19 Pages: 7007-7011
  • DOI: 10.1002/chem.201500433
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] ABC-type meso-Triaryl Substituted Subporphyrins (2014)
  • Author(s): Kota Yoshida, Hirotaka Mori, Takayuki Tanaka, Tadashi Mori, Atsuhiro Osuka
  • Journal Title: European Journal of Organic Chemistry Volume: なし Issue: 19 Pages: 3997-4004
  • DOI: 10.1002/ejoc.201402435
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Probing the Rotational Dynamics of meso-(2-Substituted)aryl Substituents in A2B-type Subporphyrins (2014)
  • Author(s): K. Yoshida, G. Copley, H. Mori, and A. Osuka
  • Journal Title: Chem. Eur. J. Volume: 20 Issue: 32 Pages: 10065-10072
  • DOI: 10.1002/chem.201402778
  • Peer Reviewed
• [Journal Article] Nucleophilic Aromatic Substitution Reactions of meso-Bromosubporphyrin: Synthesis of A Thiopyrane-Fused Subporphyrin (2014)
  • Author(s): Daiki Shimizu, Hirotaka Mori, Masaaki Kitano, Won-Young Cha, Juwon Oh, Takayuki Tanaka, Dongho Kim, Atsuhiro Osuka
  • Journal Title: Chemistry – A European Journal Volume: 20 Issue: 49 Pages: 16194-16202
  • DOI: 10.1002/chem.201405110
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Diprotonated [28] Hexaphyrins (1.1. 1.1. 1.1) : Triangular Antiaromatic Macrocycles (2014)
  • Author(s): S. -i. Ishida, T. Higashino, S. Mori, H. Mori, N. Aratani, T, Tanaka, J. M. Lim, D. Kim, A. Osukat
  • Journal Title: Angewandte Chemie International Edition Volume: 53 Issue: 13 Pages: 3427-3431
  • DOI: 10.1002/anie.201400301
  • Peer Reviewed
• [Journal Article] Gold (III)-Iridium (III) Hybrid Complexes of Hexaphyrin (1.1. 1.1. 1) (2013)
  • Author(s): K. Naoda, H. Hori, A. Osuka
  • Journal Title: Chemistry-An Asian Journal Volume: 8 Issue: 7 Pages: 1395-1398
  • DOI: 10.1002/asia.201300320
  • Peer Reviewed
• [Journal Article] Bottom-Up Synthesis of Bis (triisopropylsilyI) ethynyl Hexaphyrin Bearing an Unsubstitutod meso-Carbon (2013)
  • Author(s): H. Mori, K. Naoda, A. Osuka
  • Journal Title: Asian Journal of Organic Chemistry Volume: 2 Issue: 7 Pages: 600-605
  • DOI: 10.1002/ajoc.201300061
  • Peer Reviewed
• [Journal Article] The Marriage of Peripherally Metallated and Directly Linked Porphyrins : Bromidobis (phosphine) platinum (II) as a Cation-Stabilizing Substituent on Directly Linked and Fused Triply Linked Diporphyrins (2013)
  • Author(s): R. D. Hartnell, T. Yoneda, H. Mori. A. Osuka, D. P. Arnold
  • Journal Title: Chemistry An Asian Journal Volume: 8 Issue: 11 Pages: 2670-2679
  • DOI: 10.1002/asia.201300633
  • Peer Reviewed
• [Journal Article] Modulation of Dual Electronic Circuits of [26] Hexaphyrins Using Internal Aromatic Straps (2013)
  • Author(s): H. Mori, J. M. Lim, D. Kim, A. Osuka
  • Journal Title: Angewandte Chemie International Edition Volume: 52 Issue: 49 Pages: 12997-13001
  • DOI: 10.1002/anie.201308545
  • Peer Reviewed
• [Presentation] 近赤外領域に強い光吸収を示すメゾオリゴチエニル置換ポルフィリンの合成と物性 (2015)
  • Author(s): 森裕貴、大須賀篤弘
  • Organizer: 日本化学会秋期事業 第5回 CSJフェスタ2015
  • Place of Presentation: 東京都、船堀タワーホール
  • Year and Date: 2015-10-13
• [Presentation] 近赤外領域に強い光吸収を示すメゾオリゴチエニル置換ポルフィリンの合成と物性 (2015)
  • Author(s): 森裕貴、大須賀篤弘
  • Organizer: 第26回 基礎有機化学討論会
  • Place of Presentation: 愛媛県、愛媛大学
  • Year and Date: 2015-09-24
• [Presentation] 非環状らせん共役系を有するヘキサフィリンの合成と物性 (2015)
  • Author(s): 森 裕貴, 鈴木 優章, 大須賀 篤弘
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学（千葉）
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] 非環状らせん共役系を有する26πヘキサフィリンの合成と物性 (2014)
  • Author(s): 森 裕貴, 大須賀 篤弘
  • Organizer: 第25回 基礎有機化学討論会
  • Place of Presentation: 東北大学（宮城）
  • Year and Date: 2014-09-07 – 2014-09-09
• [Presentation] Synthesis and Characterization of Porphyrin–Hexaphyrin Hybrid Arrays (2014)
  • Author(s): Hirotaka Mori, Takayuki Tanaka, Atsuhiro Osuka
  • Organizer: 8th International Conference on Porphyrin and Phthalocyanines
  • Place of Presentation: イスタンブール（トルコ）
  • Year and Date: 2014-07-22 – 2014-07-27
• [Presentation] ポルフィリン-ヘキサフィリンハイブリッド多量体の合成と物性 (2014)
  • Author(s): 森 裕貴, 田中 隆行, 大須賀 篤弘
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学(愛知県)
  • Year and Date: 2014-03-29
• [Presentation] Synthesis and Properties of Porphyrin-Hexaphyrin-Porphyrin Triads (2014)
  • Author(s): Hirotaka Mori and Atsuhiro Osuka
  • Organizer: 2014 KAIST-KYOTO-NTHU Junior Chemist Symposium
  • Place of Presentation: Paejeon (Korea)
  • Year and Date: 2014-02-11
• [Presentation] ポルフィリン-ヘキサフィリンハイブリッド多量体の合成と物性 (2013)
  • Author(s): 森 裕貴, 大須賀 篤弘
  • Organizer: 第24回基礎有機化学討論会
  • Place of Presentation: 学習院大学(東京都)
  • Year and Date: 2013-09-07
• [Presentation] Synthesis and Characterization of Porphyrin-Hexaphyrin-Porphyrin Triads (2013)
  • Author(s): Hirotaka Mori and Atsuhiro Osuka
  • Organizer: 15th International Symposium on Novel Arometic Compounds (ISNA15)
  • Place of Presentation: Taipei (Taiwan)
  • Year and Date: 2013-08-01
• [Presentation] Synthesis and Characterization of Porphyrin-Hexaphyrin-Porphyrin Triad (2013)
  • Author(s): Hirotaka Mori and Atsuhiro Osuka
  • Organizer: Challenges in Organic Materials and Supramolecular Chemistry in the International Symposia on Advancing the Chemical Sciences (ISACSlO)
  • Place of Presentation: Kyoto University (Japan)
  • Year and Date: 2013-06-21
• [Remarks] 京都大学大学院理学研究科化学専攻 集合有機分子機能研究室 ホームページ
  • URL: http://kuchem.kyoto-u.ac.jp/shuyu/
• [Remarks] 研究室ホームページ
  • URL: http://kuchem.kyoto-u.ac.jp/shuyu/